Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
  • H01G9/004—Details
  • H01G9/022—Electrolytes; Absorbents
  • H01G9/035—Liquid electrolytes, e.g. impregnating materials
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
  • H01G9/145—Liquid electrolytic capacitors
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
  • H01G9/15—Solid electrolytic capacitors
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/13—Energy storage using capacitors

Definitions

• the present invention relates to an electrolytic solution for electrolytic capacitors, an electrolytic capacitor using the electrolytic solution, and a hybrid electrolytic capacitor.
• electrolytic capacitors and hybrid aluminum electrolytic capacitors that use an electrolyte that uses polyhydric alcohols such as ethylene glycol, which has a high boiling point, as a solvent and has low permeability to the sealing rubber.
• polyhydric alcohols such as ethylene glycol, which has a high boiling point, as a solvent and has low permeability to the sealing rubber.
• problems such as a decrease in the conductivity of the electrolytic solution due to an esterification reaction between a polyhydric alcohol and a carboxylic acid as an electrolyte at high temperatures, and deterioration of the conductive polymer due to an increase in pH. .
• Patent Document 1 a structure in which a linear alkyl group having 3 or more carbon atoms is bonded to one of the carbon atoms of a carboxylic acid and a ketone group, and a branched alkyl group is bonded to the other
• An electrolytic solution containing a compound having Patent Document 2 proposes an electrolytic solution using a salt of phosphonic acid or phosphinate anion and 1,2,3,4-tetramethylimidazolinium as the electrolyte.
• the electrolytic solution using the ketone group-containing compound described in Patent Document 1 cannot completely inhibit the esterification, so it is not a sufficient solution.
• the protection of aluminum oxide, which is the anode foil of the electrolytic capacitor is insufficient. Therefore, there is a problem that aluminum oxide is corroded by the electrolytic solution when stored at high temperature for a long period of time.
• An object of one aspect of the present invention is to provide an electrolytic solution with high initial conductivity, little change over time, and reduced corrosion of capacitor members.
• Another aspect of the present invention aims to provide an electrolytic capacitor and a hybrid electrolytic capacitor using the electrolytic solution, which have a low initial ESR (equivalent series resistance) and a small change over time.
• the present inventors arrived at the present invention as a result of conducting studies to achieve the above objectives.
• one aspect of the present invention is an electrolytic solution for an electrolytic capacitor containing an acid component (A), a base component (B) and an organic solvent (C),
• the acid component (A) contains an acid component (A1) represented by the following general formula (1) and/or an acid component (A2) represented by the following general formula (2),
• the total content of the acid component (A1) and the acid component (A2) is 50% by weight or more based on the weight of the acid component (A)
• the electrolytic solution for an electrolytic capacitor wherein the basic component (B) contains at least one component selected from the group consisting of ammonium, primary amine (B1), secondary amine (B2) and tertiary amine (B3).
• Another aspect of the present invention is an electrolytic capacitor and a hybrid electrolytic capacitor using the electrolytic solution.
• X represents a hydrocarbon group optionally having a hydroxyl group having 3 to 20 carbon atoms
• Y represents a hydrogen atom, a hydrocarbon having 1 to 10 carbon atoms optionally having a hydroxyl group, group or a residue obtained by removing one hydrogen atom from the hydroxyl group of polyalkylene glycol.
• two Zs independently represent a hydrocarbon group having 1 to 6 carbon atoms.
• an electrolytic solution with high initial conductivity, little change over time, and reduced corrosion of capacitor members.
• an electrolytic capacitor and a hybrid electrolytic capacitor using the electrolytic solution which have a low initial ESR and a small change over time.
• the acid component (A) contained in the electrolytic solution according to one embodiment of the present invention is the acid component (A1) represented by the general formula (1) and/or the acid component (A2) represented by the general formula (2) )including.
• X has 3 to 20 carbon atoms, preferably 4 to 8 carbon atoms, and particularly preferably 6 from the viewpoint of electrical conductivity and aluminum corrosiveness.
• Y is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a hydroxyl group, or a residue obtained by removing one hydrogen atom from a hydroxyl group of polyalkylene glycol. From the point of view, it is preferably a hydrogen atom.
• Examples of the acid component (A1) include (n-propyl)phosphonic acid, (iso-propyl)phosphonic acid, (n-butyl)phosphonic acid, (iso-butyl)phosphonic acid, (tert-butyl)phosphonic acid, pentyl Phosphonic acid, hexylphosphonic acid, phenylphosphonic acid, (4-hydroxyphenyl)phosphonic acid, heptylphosphonic acid, octylphosphonic acid (n-octylphosphonic acid, etc.), n-icosanephosphonic acid, dehydration of phenylphosphonic acid and methanol
• Examples include condensates, dehydrated condensates of phenylphosphonic acid and ethanol, dehydrated condensates of phenylphosphonic acid and ethylene glycol, dehydrated condensates of phenylphosphonic acid and glycerin, and dehydrated condensates of phenylphosphonic acid and polyethylene glycol.
• polyethylene glycol that undergoes dehydration condensation with phenylphosphonic acid examples include diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, and heptaethylene glycol.
• the acid component (A1) may be used singly or in combination of two or more.
• two Z's each independently represent a hydrocarbon group having 1 to 6 carbon atoms.
• the number of carbon atoms in Z is preferably 2 to 6, particularly preferably 4 to 6, from the viewpoint of electrical conductivity and aluminum corrosiveness.
• Examples of the acid component (A2) include dimethylphosphinic acid, diethylphosphinic acid, di(n-propyl)phosphinic acid, di(iso-propyl)phosphinic acid, di(n-butyl)phosphinic acid, and di(iso-butyl).
• phosphinic acid di(tert-butyl)phosphinic acid, dipentylphosphinic acid, dihexylphosphinic acid, diphenylphosphinic acid, methylethylphosphinic acid, methyl (n-propyl)phosphinic acid, methyl (iso-propyl)phosphinic acid, methyl (n -butyl)phosphinic acid, methyl (iso-butyl)phosphinic acid, methyl (tert-butyl)phosphinic acid, methylpentylphosphinic acid, methylhexylphosphinic acid, methylheptylphosphinic acid, methyloctylphosphinic acid, ethyl (n-propyl) phosphinic acid, ethyl (iso-propyl)phosphinic acid, ethyl (n-butyl)phosphinic acid, ethyl (
• the acid component (A2) may be used singly or in combination of two or more.
• the acid component (A1) is preferred from the viewpoint of electrical conductivity and aluminum corrosiveness, and more preferably (n-butyl)phosphonic acid, (iso-butyl)phosphonic acid, (tert- butyl)phosphonic acid, pentylphosphonic acid, hexylphosphonic acid, phenylphosphonic acid, (4-hydroxyphenyl)phosphonic acid, (4-hydroxyphenyl)phosphonic acid, one or more selected from the group consisting of heptylphosphonic acid and octylphosphonic acid, particularly preferably phenyl Phosphonic acid.
• the acid component (A) in one embodiment of the present invention may also contain an acid component (A3) other than the acid components (A1) and (A2).
• the acid component (A3) include carboxylic acids, phosphonic acids other than the acid component (A1), phosphinic acids, and sulfonic acids.
• Carboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, 2-methylazeleic acid, sebacic acid, 1,5-octanedicarboxylic acid, 4,5- octanedicarboxylic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,6-decanedicarboxylic acid, 5,6-decanedicarboxylic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and the like. be done.
• Phosphonic acids and phosphinic acids other than the acid component (A1) include methylphosphonic acid, ethylphosphonic acid, n-henicosanephosphonic acid, hypophosphorous acid, diheptylphosphinic acid, dioctylphosphinic acid, dinonylphosphinic acid and the like. mentioned.
• Sulfonic acids include alkylsulfonic acid (methylsulfonic acid, ethylsulfonic acid, etc.), benzenesulfonic acid and alkylbenzenesulfonic acid (toluenesulfonic acid, dodecylbenzenesulfonic acid, etc.).
• the total content of the acid component (A1) and the acid component (A2) is 50% by weight or more based on the weight of the acid component (A), and preferably 80% by weight or more from the viewpoint of stability over time. , more preferably 95% by weight or more, and particularly preferably 100% by weight.
• the content of the acid component (A) in one embodiment of the present invention is preferably 1 to 20% by weight, more preferably 3 to 17% by weight, based on the weight of the electrolytic solution for electrolytic capacitors, from the viewpoint of adjusting the pH of the solution. % by weight.
• the base component (B) in one embodiment of the present invention contains at least one component selected from the group consisting of ammonium, primary amine (B1), secondary amine (B2) and tertiary amine (B3).
• Examples of the primary amine (B1) include methylamine, ethylamine, propylamine, isopropylamine and cyclohexylamine.
• Secondary amines (B2) include dimethylamine, diethylamine, methylethylamine, methylpropylamine, methylisopropylamine, morpholine, N-methyl-N-[2-(N'-methylamino)propyl]acetamide, N-methyl -N-[2-(N'-methylamino)-1-methylethyl]acetamide, N-ethyl-N-[2-(N'-methylamino)ethyl]acetamide, N-methyl-N-[2- (N'-methylamino)ethyl]acetamide, N-methyl-N-[2-(N'-ethylamino)propyl]acetamide, N-ethyl-N-[2-(N'-methylamino)-1- methylethyl]acetamide, N-methyl-N-[2-(N'-methylamino)ethyl]propionamide and N-methyl-N-[2-(N'
• Tertiary amines (B3) include trimethylamine, triethylamine, dimethylethylamine, dimethylpropylamine, dimethylisopropylamine, triethanolamine, pyridine, 4-methylmorpholine, 4-ethylmorpholine, 4-(2-hydroxyethyl)morpholine, 4-(2-hydroxypropyl)morpholine, ethylene oxide adduct of cyclohexylamine, propylene oxide adduct of cyclohexylamine, and the like.
• the total content of ammonium, primary amine (B1), secondary amine (B2) and tertiary amine (B3) is preferably based on the weight of the electrolytic solution for electrolytic capacitors. It is 0.01 to 15% by weight, more preferably 1 to 10% by weight.
• the base component (B) may contain a base component (B4) other than ammonium, primary amine (B1), secondary amine (B2) and tertiary amine (B3).
• Examples of the base component (B4) include quaternary ammonium and amidinium.
• quaternary ammonium examples include tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium and tetraethylammonium.
• amidinium examples include imidazolinium and cations in which the hydrogen atoms of imidazolinium are substituted with alkyl groups (1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, , 1,3-dimethyl-2,4-diethylimidazolinium and 1,2-dimethyl-3,4-diethylimidazolinium, etc.), imidazolium, and cations in which hydrogen atoms of imidazolium are substituted with alkyl groups (1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium, 1,2,3-trimethylimidazolium, etc.) and the like.
• the base component (B) may contain two or more of these base components.
• base components (B) from the viewpoint of thermal stability, preferably one or more selected from the group consisting of secondary amines (B2) and tertiary amines (B3), more preferably tertiary Amine (B3).
• the content of the base component (B) in one embodiment of the present invention is preferably 0.1 to 15% by weight, more preferably 0.1 to 15% by weight, based on the weight of the electrolytic solution for electrolytic capacitors, from the viewpoint of adjusting the pH of the electrolytic solution. is 1 to 10% by weight.
• Organic solvent (C) in one embodiment of the present invention preferably contains at least one component selected from polyhydric alcohols, sulfone compounds, lactone compounds and carbonate compounds.
• polyhydric alcohols examples include alkylene glycol, glycerin components and sugar alcohols.
• Alkylene glycol includes ethylene glycol, propylene glycol, and polyalkylene glycol having a repeating structure of alkylene oxide.
• Alkylene oxides include, for example, ethylene oxide, propylene oxide, trimethylene oxide, and butylene oxide.
• the polyalkylene glycol may contain one type of alkylene oxide unit, or may contain two or more types of alkylene oxide units. Examples of polyalkylene glycols include polyethylene glycols (diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, etc.).
• glycerin components include glycerin, alkylene oxide adducts of glycerin, polyglycerin, and alkylene oxide adducts of polyglycerin.
• Sugar alcohols include tetritol, pentitol, mannitol, sorbitol, heptitol and octitol.
• Sulfone compounds include sulfolane, dimethylsulfoxide and diethylsulfoxide.
• Lactone compounds include ⁇ -butyrolactone and ⁇ -valerolactone.
• carbonate compounds include dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, ethylene carbonate, propylene carbonate and fluoroethylene carbonate.
• the organic solvent (C) may contain two or more of these organic solvents.
• organic solvents (C) from the viewpoint of preventing dry-up of the electrolytic solution, polyhydric alcohols are preferable, alkylene glycol, glycerin components and sugar alcohols are more preferable, and alkylene glycol and glycerin are particularly preferable. and most preferably ethylene glycol.
• the content of the polyhydric alcohol is preferably 50% by weight or more, more preferably 50% by weight or more, based on the weight of the organic solvent (C), from the viewpoint of suppressing dry-up of the electrolytic solution. is 90% by weight or more, particularly preferably 100% by weight.
• the content of the organic solvent (C) in one embodiment of the present invention is preferably 50 to 98% by weight, more preferably 70% by weight, based on the weight of the electrolytic solution for electrolytic capacitors, from the viewpoint of the viscosity of the electrolytic solution. ⁇ 96% by weight.
• the electrolytic solution for an electrolytic capacitor according to one embodiment of the present invention may or may not contain water, if necessary.
• the content of water is preferably 10% by weight or less, more preferably 5% by weight or less, based on the weight of the electrolytic solution for electrolytic capacitors, from the viewpoint of preventing swelling of the capacitor. Preferably, it is 0.3% by weight or less.
• additives commonly used in electrolytic solutions can be added to the electrolytic solution for electrolytic capacitors according to one embodiment of the present invention, if necessary.
• the additive include boric acid derivatives (for example, boric acid, complex compounds of boric acid and polysaccharides [mannitol, sorbit, etc.], complex compounds of boric acid and polyhydric alcohols [ethylene glycol, glycerin, etc.], etc.). ), nitro compounds (eg, o-nitrobenzoic acid, p-nitrobenzoic acid, m-nitrobenzoic acid, o-nitrophenol, p-nitrophenol, etc.).
• boric acid derivatives for example, boric acid, complex compounds of boric acid and polysaccharides [mannitol, sorbit, etc.], complex compounds of boric acid and polyhydric alcohols [ethylene glycol, glycerin, etc.], etc.
• nitro compounds eg, o-nitrobenzoic acid, p-nitrobenzoic acid, m-
• the amount added is preferably 5% by weight or less, particularly preferably 5% by weight or less, based on the total weight of the acid component (A), the base component (B) and the organic solvent (C). is 2% by weight or less.
• the electrolytic solution for electrolytic capacitors according to one embodiment of the present invention is suitable for electrolytic capacitors and hybrid electrolytic capacitors.
• An electrolytic capacitor according to one embodiment of the present invention has a capacitor element, a pair of lead wires, and an exterior body.
• a pair of lead wires are each connected to a capacitor element.
• the outer package encloses the capacitor element with the other end of the lead wire led out to the outside.
• the exterior body is composed of a cylindrical case and a sealing body.
• a capacitor element impregnated with an electrolytic solution is housed in this case, and a pair of lead wires are inserted through the through-holes of the sealing member, respectively, and compressed by a drawn portion provided on the outer peripheral surface of the case, thereby forming an exterior body. Seal.
• a capacitor element in one embodiment of the present invention has an anode foil having a dielectric layer on its surface.
• the anode foil is formed by roughening the surface of an aluminum foil by edging, and then chemically converting the surface of the roughened aluminum foil with an anodic oxide film, which is a dielectric.
• the capacitor element In addition to the anode foil, the capacitor element also has a cathode foil and a separator.
• a capacitor element is formed by laminating and winding an anode foil, a cathode foil, and a separator.
• the electrolytic solution enters the capacitor element formed as described above, and an electrolytic capacitor is produced.
• a hybrid electrolytic capacitor according to one embodiment of the present invention is formed from a capacitor element having a dielectric layer of anode foil and a layer of solid electrolyte in contact with the dielectric layer.
• This solid electrolyte is, for example, a conductive polymer such as polythiophene and its derivatives (poly3,4-ethylenedioxythiophene, polypyrrole, etc.).
• the solid electrolyte is preferably poly-3,4-ethylenedioxythiophene.
• a dopant is incorporated into this conductive polymer, and the dopant plays a role in developing conductivity.
• Typical dopants are acids such as p-toluenesulfonic acid, polystyrenesulfonic acid and the like.
• a hybrid electrolytic capacitor according to one embodiment of the present invention has a capacitor element, a pair of lead wires, and an exterior body.
• a pair of lead wires are each connected to a capacitor element.
• the outer package encloses the capacitor element with the other end of the lead wire led out to the outside.
• the exterior body is composed of a cylindrical case and a sealing body.
• a capacitor element impregnated with an electrolytic solution is housed in this case, and a pair of lead wires are inserted through the through-holes of the sealing member, respectively, and compressed by a drawn portion provided on the outer peripheral surface of the case, thereby forming an exterior body. Seal.
• a hybrid electrolytic capacitor according to one embodiment of the present invention has an anode foil having a dielectric layer on its surface and a solid electrolyte layer in contact with the dielectric layer of the anode foil.
• the anode foil is formed by roughening the surface of aluminum foil by edging, and then chemically treating the surface with an anodic oxide film, which is a dielectric.
• the capacitor element In addition to the anode foil, the capacitor element also has a cathode foil and a separator.
• a capacitor element is formed by laminating and winding an anode foil, a cathode foil, and a separator. Then, a solid electrolyte layer containing a conductive polymer is formed between the anode foil and the cathode foil.
• Methods for producing the solid electrolyte layer include a method of impregnating the layer with a conductive polymer solution and then drying, and a method of electrolytically polymerizing the conductive polymer.
• the electrolytic solution enters the gaps of the solid electrolyte formed in the capacitor element formed as described above, and a hybrid electrolytic capacitor is produced.
• the present invention may include the following configurations.
• An electrolytic solution for an electrolytic capacitor containing an acid component (A), a base component (B) and an organic solvent (C)
• the acid component (A) contains an acid component (A1) represented by the following general formula (1) and/or an acid component (A2) represented by the following general formula (2),
• the total content of the acid component (A1) and the acid component (A2) is 50% by weight or more based on the weight of the acid component (A)
• the electrolytic solution for an electrolytic capacitor, wherein the base component (B) contains at least one component selected from the group consisting of ammonium, primary amine (B1), secondary amine (B2) and tertiary amine (B3).
• X represents a hydrocarbon group optionally having a hydroxyl group having 3 to 20 carbon atoms
• Y represents a hydrogen atom, a hydrocarbon having 1 to 10 carbon atoms optionally having a hydroxyl group, group or a residue obtained by removing one hydrogen atom from the hydroxyl group of polyalkylene glycol.
• two Zs independently represent a hydrocarbon group having 1 to 6 carbon atoms.
• the organic solvent (C) contains at least one component selected from the group consisting of polyhydric alcohols, sulfone compounds, lactone compounds and carbonate compounds.
• ⁇ 3> The electrolytic solution for an electrolytic capacitor according to ⁇ 1> or ⁇ 2>, wherein the organic solvent (C) contains a polyhydric alcohol.
• the organic solvent (C) contains a polyhydric alcohol.
• ⁇ 4> Any one of ⁇ 1> to ⁇ 3> that does not contain water, or if water is contained, the content of water is 10% by weight or less based on the weight of the electrolytic solution for electrolytic capacitors.
• ⁇ 5> The electrolytic solution for electrolytic capacitors according to any one of ⁇ 1> to ⁇ 4>, wherein the content of the acid component (A) is 1 to 20% by weight based on the weight of the electrolytic solution for electrolytic capacitors. .
• ⁇ 6> The electrolytic solution for an electrolytic capacitor according to any one of ⁇ 1> to ⁇ 5>, wherein the acid component (A) is the acid component (A1).
• the base component (B) contains one selected from the group consisting of secondary amines (B2) and tertiary amines (B3).
• the content of the basic component (B) is 0.1 to 15% by weight based on the weight of the electrolytic solution for electrolytic capacitors. Electrolyte.
• ⁇ 9> The electrolytic solution for electrolytic capacitors according to ⁇ 1> to ⁇ 8>, wherein the content of the organic solvent (C) is 50 to 98% by weight based on the weight of the electrolytic solution for electrolytic capacitors.
• a hybrid electrolytic capacitor comprising the electrolytic solution for electrolytic capacitors according to any one of ⁇ 1> to ⁇ 9> and a solid electrolyte layer.
• P2 was defined as the pH of the electrolytic solution after being held at 145°C.
• a value of P2-P1 was obtained as the amount of pH change.
• An anode foil, a cathode foil, and a separator each having a dielectric layer of an aluminum oxide film on its surface are cut into a given width and length. Then, connect the lead wires to the anode and cathode by caulking.
• Capacitor elements were impregnated with the above electrolytic solutions (EL1 to EL22, R1 to R9), stored in a case, and crimped to complete an electrolytic capacitor.
• the electrolytic capacitor was held for 2000 hours while applying the rated voltage at 145°C. After that, the ESR (ESR after being left at high temperature) was measured in a 20° C. environment in the same procedure as the initial ESR. A ratio of the ESR of the electrolytic capacitor after being held at 145° C. to the initial ESR (ESR after being left at high temperature/initial ESR) was obtained.
• hybrid electrolytic capacitor ⁇ Examples 45 to 66 (Hybrid Electrolytic Capacitors HA1 to HA22) and Comparative Examples 19 to 27 (Comparative Electrolytic Capacitors HR1 to HR9)> Using the electrolytic solution for electrolytic capacitors described above, a hybrid electrolytic capacitor is produced in the following procedure.
• An anode foil, a cathode foil, and a separator each having a dielectric layer of an aluminum oxide film on its surface are cut into pieces of constant width and length. Then, connect the lead wires to the anode and cathode by caulking.
• Capacitor elements were impregnated with the above electrolytic solutions (EL1 to EL22, R1 to R9), stored in a case, and crimped to complete a capacitor.
• PEDOT was used for the solid electrolyte layer.
• the hybrid electrolytic capacitor was held for 2000 hours while applying the rated voltage at 145°C. After that, the ESR (ESR after being left at high temperature) was measured in a 20° C. environment in the same procedure as the initial ESR. As the ESR increase rate, the ratio of the ESR of the hybrid electrolytic capacitor after being held at 145° C. to the initial value (ESR after being left at high temperature/initial ESR) was obtained.
• the electrolytic solutions of Examples 1 to 22 according to one embodiment of the present invention are excellent in high initial conductivity, and corrosion is reduced (no corrosion of the foil, no corrosion of the edge of the foil) Only a slight discoloration was observed in some areas), and the change in pH and conductivity was small even after standing at high temperature.
• the electrolytic capacitors and hybrid electrolytic capacitors of Examples 23 to 66 according to one embodiment of the present invention are excellent in ESR with low ESR, and there is no change in ESR even after being left at high temperature. small.
• the electrolytic capacitors of Comparative Examples 10 to 14 and Comparative Examples 17 to 18 and the hybrid electrolytic capacitors of Comparative Examples 19 to 23 and Comparative Examples 26 to 27 show changes in ESR after being left at high temperatures. was big.
• the electrolytic capacitors of Comparative Examples 15 and 16 and the hybrid electrolytic capacitors of Comparative Examples 24 and 25 had high initial ESR. Thus, none of the electrolytic capacitors and hybrid electrolytic capacitors of the comparative examples achieved a low ESR with little change over time.
• electrolytic solution By using the electrolytic solution according to one embodiment of the present invention, it is possible to realize an electrolytic solution with high initial conductivity, little change over time, and reduced corrosion of capacitor members. In addition, electrolytic capacitors and hybrid electrolytic capacitors with low initial ESR and little change over time can also be realized. Therefore, the market value of the electrolytic solution of the present invention is very large as the life of the power supply used in the market is becoming longer.
• the electrolytic solution according to one embodiment of the present invention is particularly useful for electrolytic capacitors and hybrid electrolytic capacitors for power sources for automotive electrical equipment and digital home appliances.

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